Production of Aromatics from Methanol Using Selective Hydrogen Combustion

ABSTRACT

A catalyst system and processes for combined aromatization and selective hydrogen combustion of oxygenated hydrocarbons are disclosed. The catalyst system contains at least one aromatization component and at least one selective hydrogen combustion component. The process is such that the yield of hydrogen is less than the yield of hydrogen when contacting the hydrocarbons with the aromatization component alone.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.14/876,952, filed on Oct. 7, 2015, and entitled, “Production ofAromatics from Methanol Using Selective Hydrogen Combustion,” whichclaims priority to and the benefit of U.S. Provisional Application Ser.No. 62/082,668 filed Nov. 21, 2014, and entitled, “Production ofAromatics From Methanol Using Selective Hydrogen Combustion,” thecontents of each being incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to a catalyst system and its use inprocesses involving aromatization of oxygenated hydrocarbons. Thecatalyst system is particularly useful in reducing the concentration ofhydrogen in aromatization products.

BACKGROUND OF THE INVENTION

Conversion of various feeds to aromatic compounds is an industriallyvaluable process. Some conventional methods can include conversion ofmethanol and/or olefins to aromatics in the presence of a molecularsieve, such as ZSM-5. Reactions for conversion of methanol and/orolefins to aromatics can be useful, for example, for creation ofaromatics as individual products, or for formation of aromatic andolefin mixtures for use as naphtha boiling range or distillate boilingrange fuels.

U.S. Pat. Nos. 4,049,573 and 4,088,706 disclose that methanol can beconverted to a hydrocarbon mixture rich in C₂-C₃ olefins and mononucleararomatics, particularly p-xylene, by contacting the methanol at atemperature of 250-700° C. and a pressure of 0.2 to 30 atmospheres witha crystalline aluminosilicate zeolite catalyst which has a ConstraintIndex of 1-12 and which has been modified by the addition of an oxide ofboron or magnesium either alone or in combination or in furthercombination with oxide of phosphorus. The above-identified disclosuresare incorporated herein by reference.

Methanol can be converted to gasoline employing the MTG (methanol togasoline) process. The MTG process is disclosed in the patent art,including, for example, U.S. Pat. Nos. 3,894,103; 3,894,104; 3,894,107;4,035,430 and 4,058,576. U.S. Pat. No. 3,894,102 discloses theconversion of synthesis gas to gasoline. MTG processes provide a simplemeans of converting syngas to high-quality gasoline. The ZSM-5 catalystused is highly selective to gasoline under methanol conversionconditions, and is not known to produce distillate range fuels, becausethe C₁₀+ olefin precursors of the desired distillate are rapidlyconverted via hydrogen transfer to heavy polymethylaromatics and C₄ toC₈ isoparaffins under methanol conversion conditions.

Chinese Patent No. 1,220,288 describes a methanol conversion toaromatics (“MTA”) technology. The MTA technology makes use of modifiedzeolite catalysts to convert methanol to liquid hydrocarbon productscontaining aromatics.

Solid oxygen carrier selective hydrogen combustion (“SHC”) catalysts areunique materials where oxygen used to oxidize hydrogen is bound up inthe lattice of the catalysts. Due to size exclusion, these materialshave been found to be very selective to react with hydrogen alone. Forexample, U.S. Pat. No. 5,430,210 incorporated herein by referencedescribes contacting a hydrocarbon and hydrogen stream and an oxygencontaining stream with separate surfaces of a metal oxide membraneimpervious to non-oxygen containing gases. The metal oxide membrane wasselective for hydrogen combustion.

Grasselli et al., Catalytic dehydrogenation (DH) of light paraffinscombined with selective hydrogen combustion (SHC), Appl. Catal. A 189(1999) 1, pp. 1-8, described conversion of propane to propylene that wastwice the thermodynamic limit with selectivity to propylene in excess of90% using Bi₂O₃ as an SHC catalyst mixed with platinum-based propylenedehydrogenation catalyst. The process operated on intermittent feedcycles of propane and air to regenerate the catalyst. While initialconversion data was promising, the Bi₂O₃ catalyst was not stable.

Methanol conversion to aromatics is non-selective and exothermic.Insufficient heat removal can lead to run-away temperature excursionsthat negatively affect aromatic selectivity. There is an ongoing desireto improve methods of converting methanol to aromatics that yield ahigher amount of aromatics and are less prone to temperature excursionsthan prior art methods.

SUMMARY OF THE INVENTION

The present invention provides methods for improving the yield ofaromatics from conversion of oxygenated hydrocarbon feed, for example,methanol. In one aspect, the invention relates to a catalyst systemcomprising at least one aromatization component and at least oneselective hydrogen combustion (“SHC”) component. The multi-componentcatalyst system permits simultaneous conversion of oxygenatedhydrocarbon feeds to aromatics and selective combustion of the resultinghydrogen to water. It is believed that selectively combusting thehydrogen produced during conversion of oxygenated hydrocarbon toaromatics shifts the thermodynamic equilibrium in favor of greateraromatic production. Additionally, the combustion of hydrogen in thepresence of the SHC component is optionally endothermic, which helpsmanage the heat generated by the exothermic conversion of the oxygenatedhydrocarbon to aromatics.

The SHC component of the catalyst system consists essentially of (a) ametal combination and (b) at least one of oxygen and sulfur. At leastone of oxygen and sulfur is chemically bound both within and between themetals. The metal combination of the SHC component is selected asfollows: i) at least one metal from group 3 and at least one metal fromgroups 4-15 of the Periodic Table of the Elements; ii) at least onemetal from groups 5-15 of the Periodic Table of the Elements, and atleast one metal from at least one of groups 1, 2, and 4 of the PeriodicTable of the Elements; iii) at least one metal from groups 1-2, at leastone metal from group 3, and at least one metal from groups 4-15 of thePeriodic Table of the Elements; and iv) two or more metals from groups4-15 of the Periodic Table of the Elements.

The aromatization component of the catalyst system comprises at leastone molecular sieve, for example, ZSM-5. A further option, thearomatization component additionally comprises a group 8-14 element or acombination of metals from the same group of the Periodic Table.

Another aspect of the invention relates to a hydrocarbon conversionprocess, comprising several steps. First, provide a flow-through reactorsystem containing a catalyst system comprising at least onearomatization component and at least one selective hydrogen combustioncomponent. Second, during a first time interval, execute the followingsub-steps: i) pass oxidant through the flow-through reactor system, ii)transfer at least a portion of the oxidant's oxygen to the selectivehydrogen combustion component for storage, iii) remove at least aportion of any coke from the catalyst system by oxidation or combustionwith the oxidant's oxygen, and iv) lessen or discontinue the passing ofthe oxidant through the flow-through reactor. Third, during a secondtime interval, execute the following sub-steps: i) pass an oxygenatedhydrocarbon feed through the flow-through reactor system, ii) convert atleast a portion of the oxygenated hydrocarbon feed to aromatics andhydrogen in the presence of at least the aromatization component of thecatalyst system, and iii) selectively combust at least a portion of thehydrogen with stored oxygen in the selective hydrogen combustioncomponent of the catalyst system to form water without substantiallycombusting any of the aromatics or any of the oxygenated hydrocarbonfeed. Finally, conduct at least a portion of a conversion productsmixture comprising aromatics and water away from the flow-throughreactor system.

Yet another aspect of the invention relates to a hydrocarbon conversionprocess comprising several steps. First, charge at least one oxygenatedhydrocarbon feed to a fluidized bed reactor. Second, charge a fluidizedcatalyst system from a catalyst regenerator to the fluidized bedreactor. The catalyst system comprises at least one aromatizationcomponent and at least one selective hydrogen combustion component.Third, catalytically convert the oxygenated hydrocarbon feed toaromatics and combust resultant hydrogen. Perform the conversion toaromatics and the hydrogen combustion in the presence of the catalystsystem to produce conversion products comprising aromatics and water,and an at least partially deactivated catalyst system. Discharge theproducts and spent catalyst system from the reactor. Fourth, separate aphase rich in the conversion products from a phase rich in thedeactivated catalyst system. Fifth, strip any retained volatileconversion products off the deactivated catalyst system with a strippingmaterial at stripping conditions to produce a stripped catalyst systemphase. Sixth, reactivate the stripped catalyst phase with oxidant in thecatalyst regenerator at regeneration conditions to produce the fluidizedcatalyst system. Recycle the fluidized catalyst system to the reactor.Finally, separate and recover the conversion products.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 schematically illustrates a flow-through reactor.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

For the purpose of this description and appended claims, the followingterms are defined:

Unless otherwise stated, all percentages, parts, ratios, and the likeare by weight.

Unless otherwise stated, a reference to an element, metal, compound, orcomponent includes the element, metal, compound, or component by itself,as well as in combination with other elements, metal, compounds, orcomponents, such as mixtures of compounds.

Further, when an amount, concentration, or other value or parameter isgiven as a list of upper preferable values and lower preferable values,this is to be understood as specifically disclosing all ranges formedfrom any pair of an upper preferred value and a lower preferred value,regardless of whether ranges are separately disclosed.

The particulars shown herein are by way of example and for purposes ofillustrative discussion of the embodiments of the present invention onlyand are presented in the cause of providing what is believed to be themost useful and readily understood description of the principles andconceptual aspects of the present invention. In this regard, no attemptis made to show structural details of the present invention in moredetail than is necessary for the fundamental understanding of thepresent invention, the description making apparent to those skilled inthe art how the several forms of the present invention may be embodiedin practice.

Unless otherwise stated, certain terms used herein shall have thefollowing meaning.

The term “olefins” shall mean non-aromatic hydrocarbons having one ormore carbon-carbon double bonds. The term “aromatics” shall meancompounds having one or more than one benzene ring. The term“unsaturate” means a hydrocarbon containing at least one carbon atomdirectly bound to another carbon atom by a double or triple bond.

The term “physical admixture” shall mean a combination of two or morecomponents obtained by mechanical (i.e., non-chemical) means. The term“chemically bound” shall mean bound via atom to atom bonds.

The term “selective hydrogen combustion” shall mean reacting hydrogenwith oxygen to form water or steam without substantially reactinghydrocarbons with oxygen to form carbon monoxide, carbon dioxide, and/oroxygenated hydrocarbons. The term “selective hydrogen combustioncatalyst” or “selective hydrogen combustion component (when the latterphrase is used to identify one component of a catalyst system) shallbroadly mean a material or materials capable of promoting orparticipating in a selective hydrogen combustion reaction, using eitherfree oxygen or lattice oxygen contained in the selective hydrogencombustion catalyst.

The term “group 3 metals” shall mean elements having atomic numbers of21, 39, 57 through 71, and 89 through 92.

The term “yield” shall mean weight of a product produced per unit weightof feed, expressed in terms of weight %.

The term “Periodic Table” or “Periodic Table of the Elements” means thePeriodic Chart of the Elements, as it appears on the inside cover of TheMerck Index, Twelfth Edition, Merck & Co., Inc., 1996.

The term “aromatization” means any process involving bothdehydrogenation and cyclization of non-cyclic hydrocarbon, includingoxygenated hydrocarbon to produce a hydrocarbon having at least onecyclic structure. The cyclic structures can be saturated or unsaturatedand include at least some aromatic structures. The term “aromatizationcatalyst” and “aromatization component” (when the latter phrase is usedto identify one component of a catalyst system) shall mean a material ormaterials capable of promoting or participating in an aromatizationreaction.

The term “residence time” means the average time duration fornon-reacting molecules (such as He, N2, Ar) having a molecular weight inthe range of 4 to 40 to traverse the reactor or a defined zone withinthe reactor.

The term “flow-through reactor” refers to a reactor design in whichfeeds and/or reaction mixtures can flow through the reactor, e.g., whereoxidant feeds, oxygenated hydrocarbon feeds, and/or reaction mixturescome into contact with a catalyst system as the feeds and/or reactionmixtures flow through the reactor.

With respect to flow-through reactors, the term “region” means alocation within the reactor, e.g., a specific volume within the reactorand/or a specific volume between a flow-through reactor and a secondreactor, such as a second flow-through reactor. With respect toflow-through reactors, the term “zone”, refers to a specific functionbeing carried out at a location within the flow-through reactor. Forexample, a “reaction zone” or “reactor zone” is a volume within thereactor for conducting at least one of aromatization and selectivehydrogen combustion or oxidation.

The term “tubular reactor” means an elongated, reactor vessel ofsubstantially any cross-section, the vessel being configured to allowfluid flow into, through, and out of the vessel, via first and secondapertures, the first and second apertures being located proximate toopposed ends of the elongated reactor vessel.

The term “fixed-bed catalytic reactor” means a reactor having at leastone bed of catalyst, wherein the catalyst is substantially retainedwithin the bed.

The present invention provides methods for improving the yield ofaromatics from conversion of oxygenated hydrocarbon feed, for example,methanol. The oxygenated hydrocarbon feed can comprise aliphaticaldehydes, carboxylic acids, carbohydrates, alcohols, ethers, acetalsand analogs. Preferably, the oxygenated hydrocarbon feed comprises anymonohydric alcohol having from 1 to 4 carbon atoms or ethers derivedfrom these alcohols. Thus, methanol, ethanol, n-propanol, isopropanol,n-butanol, sec-butanol and isobutanol may be used either alone or inadmixture with ethers derived from such alcohols. Likewise, the notedethers, e.g., methyl-ethyl ether may be similarly used. Particularlypreferred feeds are methanol, dimethyl ether and mixtures thereof.Optionally, the oxygenated hydrocarbon feed also contains C₁-C₅ alkanes,such as methane and/or propane, for conversion of at least a portion ofthe alkanes and the majority of oxygenated hydrocarbon to aromatics.

The present invention also relates to a catalyst system and its use inprocesses involving aromatization of oxygenated hydrocarbons. Thecatalyst system of the present invention comprises (1) at least onearomatization component and (2) at least one hydrogen removal component.The catalyst system of the present invention is multifunctional in thatthe aromatization component converts oxygenated hydrocarbon to aromaticsand hydrogen (among other products) and the hydrogen removal componentremoves or consumes hydrogen produced from the aromatization reactions.Removal of hydrogen improves selectivity to aromatics by shiftingequilibria in favor of unsaturated products.

Suitable hydrogen removal component of the catalyst system may beselective hydrogen combustion (“SHC”) catalyst. Selective hydrogencombustion is conversion of hydrogen to water via oxidation orcombustion without substantially reacting hydrocarbons with oxygen toform carbon monoxide, carbon dioxide, and/or oxygenated hydrocarbons. Inother words, less than 10 wt. %, preferably less than 5 wt. %, ofhydrocarbons react with oxygen to form carbon monoxide, carbon dioxide,and/or oxygenated hydrocarbons. The hydrogen removal component is notlimited to SHC catalyst for removal of hydrogen. Other suitable hydrogenremoval components include reverse water gas shift (“RWGS”) catalyst toconvert hydrogen and carbon dioxide to carbon monoxide and water. Stillother suitable hydrogen removal components include methanation catalystto convert hydrogen and carbon monoxide to methane.

The conversion of oxygenated hydrocarbon to aromatics according to theinvention involves aromatization reactions, with the main aromatizationreactions being carried out in a reaction zone section of at least onereactor. When the oxygenated hydrocarbon feed to the reactor comprisesmethanol, the aromatization reactions includes the following endothermicreactions:

9MeOH→C₆H₆ (aromatic)+C₃H₆ (olefins)+9H₂O+1.5H₂

Conversion of methanol to aromatics is exothermic and non-selective.Methane, alkanes, and other non-aromatic naphtha will be produced viaundesired side reactions besides the aromatics, olefins, and hydrogen.Additionally, some decomposition of the oxygenated hydrocarbon may occurto form CO and CO₂.

The multifunctional catalyst system permits simultaneous conversion ofoxygenated hydrocarbon feeds to aromatics and selective combustion ofthe resulting hydrogen to water. Without being bound by any theory, itis believed the kinetics of hydrogen combustion are much faster thanaromatization kinetics. It is believed this kinetic rate differencepermits the catalyst system of the present invention to performaromatization without a substantial co-production of hydrogen. It isfurther believed that removal of the hydrogen produced by thearomatization reaction (via combustion) would enable oxygenatedhydrocarbon conversion having increased aromatic selectivity.

Typically, the products from aromatization of oxygenated hydrocarbonsinclude hydrogen and other less desired side products. Hydrogen usuallyis not a desirable product due to the difficulty of separation. Inaddition, due to its low molecular weight, the presence of even amoderate quantity of H₂ in the products would consume a significantfraction of a gas compressor's and any other separation equipmentvolumetric capacities. Converting the hydrogen product into water, whichcan be easily condensed and separated via any conventional vapor-liquid,liquid-liquid, or other separation device, therefore, debottlenecks thecompressors and/or the separation equipment by freeing up the space thatwould be occupied by the hydrogen. Such newly created space could beused to increase the production of more desirable products sucharomatics. Alternatively, at a constant production level, convertinghydrogen to water can reduce the number or the size of equipment,thereby reducing the investment costs.

In accordance with the present invention, a catalyst system comprises anaromatization component and a selective hydrogen combustion component,which catalyst system, upon contact with an oxygenated hydrocarbon feed,simultaneously aromatizes the oxygenated hydrocarbon and selectivelycombusts the hydrogen produced from the aromatizing reaction.

Preferably, the yield of hydrogen is less than the yield of hydrogenwhen contacting said oxygenated hydrocarbon feed(s) with saidaromatization component alone under similar reaction conditions.Preferably, the yield of hydrogen is at least 10% less than the yield ofhydrogen when contacting said hydrocarbon feed(s) with saidaromatization component alone under similar reaction conditions. Morepreferably, the yield of hydrogen is at least 25% less, more preferablyat 50% less, even more preferably at least 75% less than the yield ofhydrogen when contacting said oxygenated hydrocarbon feed(s) with saidaromatization component alone under similar reaction conditions.

Selective hydrogen combustion could also help manage the heat producedby the aromatization of oxygenated hydrocarbon. Although the combustionof hydrogen is exothermic, the overall enthalpy for the reactionsinvolving the SHC component can be net endothermic. For example, theremoval of internal lattice oxygen required for the oxidation ofhydrogen is endothermic. The heat consumed by the removal of internallattice oxygen can be greater than the heat released by the combustionof that oxygen with hydrogen. Therefore, a net endothermic SHC componentwould be an ideal heat sink to manage the heat produced by theexothermic aromatization of oxygenated hydrocarbon feed. This couldreduce the amount of heat removal required to prevent run-awaytemperature excursions. In some aspects, the SHC component reactions canbe sufficiently endothermic that the combined aromatization componentand SHC component reactions are net endothermic.

Thus, in accordance with the present invention, a hydrocarbon conversionprocess comprises contacting an oxygenated hydrocarbon feed with acatalyst system comprising at least one aromatization component and atleast one net endothermic selective hydrogen combustion component undersuitable conditions to produce aromatics, water, and other products,wherein the conversion process is conducted with a reduction of removedheat than would be required for the conversion process using a catalystsystem without at least one net endothermic SHC component. Removed heatcan be reduced by at least 2%, preferably by over 5%, 10%, 25%, 50%,75%, or even more preferably by over 100% by using the catalyst systemof the present invention over catalyst systems without at least one netendothermic SHC component. Optionally, the SHC component reactions aresufficiently endothermic that addition of heat is required to maintainprocess conditions suitable to produce aromatics. Since aromatizationreactions are exothermic, the required heat removal or input is simplythe overall enthalpy of the reaction. Thus, it is within the skill ofone of ordinary skill in the art to calculate the required heat removalor addition based on the enthalpy of the SHC component reactions.

The selective hydrogen combustion can be conducted with the feeding offree-oxygen containing gas or by using SHC materials that contain boundor lattice oxygen. It is preferred that selective hydrogen combustion isconducted via the use of lattice oxygen stored in and released from theselective hydrogen combustion component to promote selective hydrogencombustion.

In accordance with the present invention, lattice oxygen in the SHCcomponent of the catalyst system is used as the source of oxygen for theselective hydrogen combustion reaction. Higher hydrogen combustionselectivity and less CO_(x) by-product are achievable using thisapproach as compared to co-feeding oxygen to the reactor.

While using lattice oxygen in the SHC component for hydrogen combustionis advantageous, it also has a potential problem. Over time, the latticeoxygen is consumed with a resultant loss of SHC component catalystactivity. However, the SHC component activity may be recovered byregenerating the catalyst with fresh oxidant.

When lattice oxygen in the SHC component is used as the source of oxygenfor combustion, a free-oxygen containing gas (“oxidant”) can be used toperiodically regenerate or replenish the SHC component. Typically, theoxidant includes one or more of molecular oxygen (O₂), O₂ ⁻, O₂ ^(═),ionized oxygen atoms, nitrogen oxides such as N₂O, etc. Oxidant istypically in the vapor phase at hydrocarbon conversion conditions, butthis is not required, and in certain aspects liquid and/or solid oxidantcan be used. The oxidant can comprise molecular O₂, e.g., ≥90% O₂ (molarbasis, per mole of oxidant), such as, ≥99%. For example, the oxidant cancomprise O₂ in air, or O₂ obtained or derived from air, e.g., byseparation. The oxidant can comprise (or consist essentially of, orconsist of) O₂ in air. When the oxidant comprises O₂ in air, the totalfeed generally comprises at least a portion of the air's molecularnitrogen as diluent. In other words, when the oxidant comprisesmolecular oxygen in air, other gasses in the air, such as molecularnitrogen, are considered to be diluent, and are not considered to bepart of the oxidant.

Catalyst System

One aspect of the present invention pertains to a catalyst system thatcomprises (1) at least one aromatization component and (2) at least oneselective hydrogen combustion (“SHC”) component.

The aromatization component can be in physical admixture with, orchemically bound to, the SHC component. The metals selected fromcombinations (i), (ii), (iii), or (iv) can be chemically bound, bothbetween and within the groups specified. For example, within combination(ii), it would be within the scope of the present invention for two ormore metals from groups 1 and 2 to be chemically bound to each other aswell as chemically bound to the metal(s) from groups 5-15.Alternatively, the chemical binding can be only between metals ofdifferent groups and not between metals within the same group, i.e., twoor more metals from groups 1 and 2 being in admixture with each otherbut chemically bound to the metal(s) from groups 5-15.

Aromatization Component

Suitable aromatization components are described in U.S. patentapplication Ser. No. 14/829,399, which is incorporated by reference inits entirety. Aromatization components suitable for use in the inventivecatalyst system are a composition of matter comprising a molecularsieve, such as ZSM-5. Optionally, the composition of matter can includea group 8-14 element, or combination of metals from the same group ofthe Periodic Table. The composition of matter can optionally furthercomprise phosphorus and/or lanthanum and/or other elements from groups1-2 and/or groups 13-16 of the Periodic Table that provide structuralstabilization. In this sense, the term “comprising” can also mean thatthe aromatization component can comprise the physical or chemicalreaction product of the molecular sieve and the groups 8-14 element orcombination of elements from the same group (and optionally phosphorusand/or lanthanum and/or other elements from groups 1-2 and/or groups13-16). In various aspects, the molecular sieve comprises ≥10.0 wt. % ofthe aromatization component, or ≥50.0 wt. %, or ≥90.0 wt. %, or ≥95.0wt. %, or ≥99.0 wt. %.

As used herein the term “molecular sieve” refers to crystalline ornon-crystalline materials having a porous structure. Microporousmolecular sieves typically have pores having a diameter of ≤about 2.0nm. Mesoporous molecular sieves typically have pores with diameters ofabout 2 to about 50 nm. Macroporous molecular sieves have pore diametersof >50.0 nm.

Additionally or alternatively, some molecular sieves useful herein aredescribed by a Constraint Index of about 1 to about 12. Constraint Indexis determined as described in U.S. Pat. No. 4,016,218, incorporatedherein by reference for details of the method.

Particular molecular sieves are zeolitic materials. Zeolitic materialsare crystalline or para-crystalline materials. Some zeolites arealuminosilicates comprising [SiO4] and [AlO4] units. Other zeolites arealuminophosphates (AlPO) having structures comprising [AlO4] and [PO4]units. Still other zeolites are silicoaluminophosphates (SAPO)comprising [SiO4], [AlO4], and [PO4] units.

Non-limiting examples of SAPO and ALPO molecular sieves useful hereininclude one or a combination of SAPO-5, SAPO-8, SAPO-11, SAPO-16,SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37,SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, ALPO-5, ALPO-11,ALPO-18, ALPO-31, ALPO-34, ALPO-36, ALPO-37, ALPO-46, and metalcontaining molecular sieves thereof. Of these, particularly usefulmolecular sieves are one or a combination of SAPO-18, SAPO-34, SAPO-35,SAPO-44, SAPO-56, ALPO-18, ALPO-34 and metal containing derivativesthereof, such as one or a combination of SAPO-18, SAPO-34, ALPO-34,ALPO-18, and metal containing derivatives thereof, and especially one ora combination of SAPO-34, ALPO-18, and metal containing derivativesthereof.

Additionally or alternatively, the molecular sieves useful herein may becharacterized by a ratio of Si to Al. In particular embodiments, themolecular sieves suitable herein include those having a Si/Al ratio ofabout 0.05 to 0.5, e.g., 0.05 to 0.45, 0.05 to 0.40, 0.05 to 0.35, 0.05to 0.30, 0.05 to 0.25, 0.05 to 0.20, 0.05 to 0.15, 0.05 to 0.10, 0.10 to0.50, 0.1 to 0.45, 0.10 to 0.40, 0.10 to 0.35, 0.10 to 0.30, 0.10 to0.25, 0.10 to 0.20, 0.10 to 0.15, 0.20 to 0.50, 0.2 to 0.45, 0.20 to0.40, 0.20 to 0.35, 0.20 to 0.30, or 0.20 to 0.25.

In an embodiment, the molecular sieve is an intergrowth material havingtwo or more distinct crystalline phases within one molecular sievecomposition. In particular, intergrowth molecular sieves are describedin U.S. Patent Application Publication No. 2002-0165089 andInternational Publication No. WO 98/15496, published Apr. 16, 1998, bothof which are herein fully incorporated by reference.

Particular molecular sieves useful in this invention include ZSM-5 (U.S.Pat. No. 3,702,886 and Re. 29,948); ZSM-11 (U.S. Pat. No. 3,709,979);ZSM-12 (U.S. Pat. No. 3,832,449); ZSM-22 (U.S. Pat. No. 4,556,477);ZSM-23 (U.S. Pat. No. 4,076,842); ZSM-34 (U.S. Pat. No. 4,079,095);ZSM-35 (U.S. Pat. No. 4,016,245); ZSM-48 (U.S. Pat. No. 4,397,827);ZSM-57 (U.S. Pat. No. 4,046,685); and ZSM-58 (U.S. Pat. No. 4,417,780).The entire contents of the above references are incorporated byreference herein. Other useful molecular sieves include MCM-22, PSH-3,SSZ-25, MCM-36, MCM-49 or MCM-56, with MCM-22. Still other molecularsieves include Zeolite T, ZKS, erionite, and chabazite.

Another option for characterizing a zeolite (or other molecular sieve)is based on the nature of the ring channels in the zeolite. The ringchannels in a zeolite can be defined based on the number of atomsincluded in the ring structure that forms the channel. In some aspects,a zeolite can include at least one ring channel based on a 10-memberring. In such aspects, the zeolite preferably does not have any ringchannels based on a ring larger than a 10-member ring. Examples ofsuitable framework structures having a 10-member ring channel but nothaving a larger size ring channel include EUO, FER, IMF, LAU, MEL, MFI,MFS, MTT, MWW, NES, SFG, STF, STI, TON, TUN, MRE, and PON.

In some aspects, the aromatization component can also optionally includeat least one metal selected from groups 8-14 of the Periodic Table, suchas at least two metals (i.e., bimetallic) or at least three metals(i.e., trimetallic). Typically, the total weight of the groups 8-14elements is ≥0.1 wt. % based on the total weight of the aromatizationcomponent. Typically, the total weight of the groups 8-14 element is≤about 10.0 wt. %, based on the total weight of the aromatizationcomponent. Thus, the range of the amount of the groups 8-14 elementsadded to the molecular sieve may be 0.1-10.0 wt. %, or 0.1-5.0 wt. %, or0.1-2.0 wt. %, or 0.5-2.0 wt. %. Of course, the total weight of thegroups 8-14 elements shall not include amounts attributable to themolecular sieve itself.

Additionally or alternatively, in some aspects, the aromatizationcomponent can also include at least one of phosphorous and/or lanthanumand/or other elements from groups 1-2 and/or group 13-16, such as atleast two such elements or at least three such elements. Typically, thetotal weight of the phosphorous and/or lanthanum and/or other elementsfrom groups 1-2 and/or groups 13-16 is ≥0.1 wt. % based on the totalweight of the aromatization component. Typically, the total weight ofthe phosphorous and/or lanthanum and/or other elements from groups 1-2and/or groups 13-16 is ≤about 10.0 wt. %, based on the total weight ofthe aromatization component. Of course, the total weight of thephosphorous and/or lanthanum and/or other elements from groups 1-2and/or groups 13-16 shall not include amounts attributable to themolecular sieve itself.

For the purposes of this description and claims, the numbering schemefor the Periodic Table groups corresponds to the current IUPAC numberingscheme. Therefore, a “group 4 metal” is an element from group 4 of thePeriodic Table, e.g., Hf, Ti, or Zr. The more preferred molecular sievesare SAPO molecular sieves, and metal-substituted SAPO molecular sieves.In particular embodiments, one or more group 1 elements (e.g., Li, Na,K, Rb, Cs, Fr) and/or group 2 elements (e.g., Be, Mg, Ca, Sr, Ba, andRa) and/or phosphorous and/or lanthanum may be used. One or more group7-9 element (e.g., Mn, Tc, Re, Fe, Ru, Os, Co, Rh, and Ir) may also beused. Group 10 elements (Ni, Pd, and Pt) are less commonly used inapplications for forming olefins and aromatics, as the combination of agroup 10 element in the presence of hydrogen can tend to result insaturation of aromatics and/or olefins. In some embodiments, one or moregroup 11 and/or group 12 elements (e.g., Cu, Ag, Au, Zn, and Cd) may beused. In still other embodiments, one or more group 13 elements (B, Al,Ga, In, and Ti) and/or group 14 elements (Si, Ge, Sn, Pb) may be used.In a preferred embodiment, the metal is selected from the groupconsisting of Zn, Ga, Cd, Ag, Cu, P, La, or combinations thereof. Inanother preferred embodiment, the metal is Zn, Ga, Ag, or a combinationthereof.

Particular molecular sieves and groups 2-13-containing derivativesthereof have been described in detail in numerous publications includingfor example, U.S. Pat. No. 4,567,029 (MeAPO where Me is Mg, Mn, Zn, orCo), U.S. Pat. No. 4,440,871 (SAPO), European Patent Application EP-A-0159 624 (E1APSO where E1 is Be, B, Cr, Co, Ga, Fe, Mg, Mn, Ti, or Zn),U.S. Pat. No. 4,554,143 (FeAPO), U.S. Pat. Nos. 4,822,478, 4,683,217,4,744,885 (FeAPSO), EP-A-0 158 975 and U.S. Pat. No. 4,935,216 (ZnAPSO),EP-A-0 161 489 (CoAPSO), EP-A-0 158 976 (ELAPO, where EL is Co, Fe, Mg,Mn, Ti, or Zn), U.S. Pat. No. 4,310,440 (AlPO4), U.S. Pat. No. 5,057,295(BAPSO), U.S. Pat. No. 4,738,837 (CrAPSO), U.S. Pat. Nos. 4,759,919, and4,851,106 (CrAPO), U.S. Pat. Nos. 4,758,419, 4,882,038, 5,434,326, and5,478,787 (MgAPSO), U.S. Pat. No. 4,554,143 (FeAPO), U.S. Pat. Nos.4,686,092, 4,846,956, and 4,793,833 (MnAPSO), U.S. Pat. Nos. 5,345,011and 6,156,931 (MnAPO), U.S. Pat. No. 4,737,353 (BeAPSO), U.S. Pat. No.4,940,570 (BeAPO), U.S. Pat. Nos. 4,801,309, 4,684,617, and 4,880,520(TiAPSO), U.S. Pat. Nos. 4,500,651, 4,551,236, and 4,605,492 (TiAPO),U.S. Pat. Nos. 4,824,554, 4,744,970 (CoAPSO), U.S. Pat. No. 4,735,806(GaAPSO) EP-A-0 293 937 (QAPSO, where Q is framework oxide unit [QO2]),as well as U.S. Pat. Nos. 4,567,029, 4,686,093, 4,781,814, 4,793,984,4,801,364, 4,853,197, 4,917,876, 4,952,384, 4,956,164, 4,956,165,4,973,785, 5,241,093, 5,493,066, and 5,675,050, all of which are hereinfully incorporated by reference. Other molecular sieves include thosedescribed in R. Szostak, Handbook of Molecular Sieves, Van NostrandReinhold, New York, N.Y. (1992), which is herein fully incorporated byreference. In some aspects, the molecular sieve as modified by the group8-14 element and/or a group 1-2, group 13-16, lanthanum, and/orphosphorous is a ZSM-5 based molecular sieve.

Various methods for synthesizing molecular sieves or modifying molecularsieves are described in U.S. Pat. No. 5,879,655 (controlling the ratioof the templating agent to phosphorus), U.S. Pat. No. 6,005,155 (use ofa modifier without a salt), U.S. Pat. No. 5,475,182 (acid extraction),U.S. Pat. No. 5,962,762 (treatment with transition metal), U.S. Pat.Nos. 5,925,586 and 6,153,552 (phosphorus modified), U.S. Pat. No.5,925,800 (monolith supported), U.S. Pat. No. 5,932,512 (fluorinetreated), U.S. Pat. No. 6,046,373 (electromagnetic wave treated ormodified), U.S. Pat. No. 6,051,746 (polynuclear aromatic modifier), U.S.Pat. No. 6,225,254 (heating template), International Patent ApplicationWO 01/36329 published May 25, 2001 (surfactant synthesis), InternationalPatent Application WO 01/25151 published Apr. 12, 2001 (staged acidaddition), International Patent Application WO 01/60746 published Aug.23, 2001 (silicon oil), U.S. Patent Application Publication No.2002-0055433 published May 9, 2002 (cooling molecular sieve), U.S. Pat.No. 6,448,197 (metal impregnation including copper), U.S. Pat. No.6,521,562 (conductive microfilter), and U.S. Patent ApplicationPublication No. 2002-0115897 published Aug. 22, 2002 (freeze drying themolecular sieve), which are all herein incorporated by reference intheir entirety.

SHC Component

Suitable selective hydrogen combustion components are described in U.S.Patent Application Publication No. 2004-0152586 which is incorporated byreference in its entirety. The selective hydrogen combustion (“SHC”)component consists of (a) at least one of oxygen and sulfur and (b) ametal combination selected from the group consisting of:

-   -   i) at least one metal from group 3 and at least one metal from        groups 4-15 of the Periodic Table of the Elements;    -   ii) at least one metal from groups 5-15 of the Periodic Table of        the Elements, and at least one metal from at least one of groups        1, 2, and 4 of the Periodic Table of the Elements;    -   iii) at least one metal from groups 1 and 2, at least one metal        from group 3, and at least one metal from groups 4-15 of the        Periodic Table of the Elements; and    -   iv) two or more metals from groups 4-15 of the Periodic Table of        the Elements,        wherein the at least one of oxygen and sulfur is chemically        bound both within and between the metals. It is intended that        reference to a metal from each of the noted groups would include        mixtures of metals from the respective groups. For example,        reference to one or more metals from groups 4-15 includes a        mixture of chemically bound metals from groups 4 and 15 of the        Periodic Table.

While it is intended that the SHC component consist essentially of themetals from the combination (sub-group) selected along with oxygenand/or sulfur, it is recognized that impurities may be present in themanufacturing process and that impurities from the oxygenatedhydrocarbon feed may be adsorbed or incorporated into the crystallinestructure of the SHC component. To the extent that such impurities donot render the SHC component ineffective for selective hydrogencombustion, the impurities shall be deemed to be within the scope ofthis invention.

For the purposes of description of the SHC component of this invention,metals shall be deemed to include all elements classified as alkalimetals, alkaline earth metals, transition metals, other metals, andmetalloids, excluding hydrogen from group 1; boron from group 13; carbonand silicon from group 14; and nitrogen, phosphorus, and arsenic fromgroup 15.

The preferred metals from groups 1 and 2 are any of lithium, sodium,potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium,and barium.

It is noted that rare earth elements are to be included as group 3metals. Preferably, the metal(s) from group 3 are any of scandium,yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium,gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium,and lutetium.

The metal(s) or element(s) from groups 4-15 can be any metal element ora mixture of metal elements from groups 4-15 of the Periodic Table ofthe Elements. Preferably, the metal(s) from groups 4-15 is (are) atleast one of titanium, vanadium, chromium, manganese, iron, cobalt,nickel, copper, zinc, aluminum, gallium, germanium, zirconium, niobium,molybdenum, ruthenium, rhodium, palladium, silver, indium, tin,antimony, hafnium, tantalum, tungsten, rhenium, iridium, platinum, gold,lead, and bismuth. More preferably, the metal(s) from groups 4-15 is(are) at least one of titanium, manganese, iron, cobalt, nickel, copper,zinc, aluminum, gallium, germanium, zirconium, ruthenium, rhodium,palladium, silver, indium, tin, antimony, hafnium, rhenium, iridium,platinum, gold, and bismuth.

In one embodiment of the present invention, the SHC component is acombination of oxygen and/or sulfur with one or more metals from group 3and one or more metals from groups 4-15 of the Periodic Table of theElements (hereinafter “sub-group 1”). Within sub-group 1, the preferredmetals from group 3 are at least one of scandium, yttrium, lanthanum,cerium, samarium, ytterbium and praseodymium; and the preferred metalsfrom groups 4-15 are titanium, zirconium, niobium, molybdenum, tungsten,manganese, iron, cobalt, iridium, nickel, palladium, platinum, copper,zinc, aluminum gallium, indium, germanium, tin, antimony, and bismuth.Even more preferred metal(s) from group 3 are at least one of scandium,yttrium, lanthanum, and praseodymium; and more preferred metals fromgroups 4-15 are one or more of titanium, zirconium, manganese, iron,cobalt, nickel, copper, zinc, aluminum, indium, and tin.

Examples of combinations falling within sub-group 1 of the metalcombinations are Y_(a)In_(b)Zn_(c)Mn_(d)O_(x±δ),La_(a)Mn_(b)Ni_(c)Al_(d)O_(x±δ), La_(a)Mn_(b)Al_(c)O_(x±δ),Sc_(a)Cu_(b1)Mn_(c)O_(x±δ), Sc_(a)Zn_(b)Mn_(c)O_(x±δ),La_(a)Zr_(b)O_(x±δ), Mn_(a)Sc_(b)O_(x±δ), and Pr_(a)In_(b)Zn_(c)O_(x±δ),where a, b, c, and d are each between 0 and 1, the sum of a through dequals 1 to 3, x is the sum of a through d plus 1, and δ is the vacancyconcentration or excess oxygen concentration. While oxygen is indicatedin the formulae above, it will be recognized that the positions held byoxygen could be substituted with sulfur.

In an alternative embodiment of the present invention, the SHC componentis a combination of oxygen and/or sulfur with one or more metals fromgroups 5-15 of the Periodic Table of the Elements and one or more metalsfrom at least one of groups 1, 2, and/or group 4 of the Periodic Tableof the Elements (hereinafter “sub-group 2”). Within sub-group 2, thepreferred metals from groups 5-15 are at least one of niobium,molybdenum, tungsten, manganese, iron, cobalt, iridium, nickel,palladium, platinum, copper, zinc, aluminum gallium, indium, germanium,tin, antimony, and bismuth; the preferred metals from groups 1 and 2 aresodium, potassium magnesium, calcium, strontium, and barium; and thepreferred metals from group 4 are titanium and zirconium. Even morepreferred metals from Groups 5-15 are, manganese, iron, cobalt, nickel,zinc, aluminum, indium, tin, antimony and bismuth.

Examples of combinations falling within sub-group 2 of the metalcombinations are K_(a)Ba_(b)Mn_(c)O_(x±δ), K_(a)Mg_(b)Mn_(c)O_(x±δ),Na_(a)Mg_(b)Mn_(c)O_(x±δ), Mn_(a)Mg_(b)O_(x±δ),K_(a)Sr_(b)Mn_(c)O_(x±δ), In_(a)Ca_(b)Mn_(c)O_(x±δ),Bi_(a)Ca_(b)Mn_(c)Co_(d)O_(x±δ), Bi_(a)Ca_(b)Mn_(c)Ni_(d)O_(x±δ),Ca_(a)Mn_(b)Sn_(c)Co_(d)O_(x±δ), In_(a)Mg_(b)Mn_(c)Al_(d)O_(x±δ),In_(a)Zn_(b)Mn_(c)Al_(d)O_(x±δ), Na_(a)Ba_(b)Mn_(c)O_(x±δ),Na_(a)Co_(b)Mn_(c)O_(x±δ), Ca_(a)Mn_(b)Sb_(c)O_(x±δ),Ca_(a)Mn_(b)Co_(c)Al_(d)O_(x±δ), Sr_(a)Sb_(b)Sn_(c)Mg_(d)O_(x±δ),K_(a)Co_(b)Mn_(c)O_(x±δ), Mn_(a)Mg_(b)O_(x±δ),Ni_(a)Mg_(b)Mn_(c)O_(x±δ), Mn_(a)Mg_(b)Al_(c)O_(x±δ),Mn_(a)Mg_(b)Ti_(c)O_(x±δ), Sr_(a)Sb_(b)Ca_(c)O_(x±δ),Sr_(a)Ti_(b)Sn_(c)Al_(d)O_(x±δ), Sr_(a)Mn_(b)Ti_(c)Al_(d)O_(x±δ),Ca_(a)Mn_(b)O_(x±δ), Ca_(a)Zn_(b)Al_(c)O_(x±δ),Bi_(a)Ca_(b)Mn_(c)O_(x±δ), Bi_(a)Sr_(b)Co_(c)Fe_(d)O_(x±δ),Ba_(a)Mn_(b)O_(x±δ), Ca_(a)Mn_(b)Al_(c)O_(x±δ),Ca_(a)Na_(b)Sn_(c)O_(x±δ)and Ba_(a)Zr_(b)O_(x±δ), where a, b, c, and dare each between 0 and 1, the sum of a through d equals 1 to 3, xis thesum of a through d plus 1, and δ is the vacancy concentration or excessoxygen concentration. While oxygen is indicated in the formulae above,it will be recognized that the positions held by oxygen could besubstituted with sulfur.

In another alternative embodiment of the present invention, the SHCcomponent is a combination of oxygen and/or sulfur with one or moremetals from groups 1 and 2, one or more metals from group 3, and one ormore metals from groups 4-15 of the Periodic Table of the Elements(hereinafter “sub-group 3”). Within sub-group 3, the preferred metalsfrom groups 1 and 2 are at least one of sodium, potassium, magnesium,calcium, strontium and barium; the preferred metals from group 3 are atleast one of scandium, yttrium, lanthanum, cerium, samarium, ytterbiumand praseodymium; and the preferred metals from groups 4-15 are at leastone of titanium, zirconium, niobium, molybdenum, tungsten, manganese,iron, cobalt, iridium, nickel, palladium, platinum, copper, zinc,aluminum gallium, indium, germanium, tin, antimony, and bismuth. Evenmore preferred metals from groups 1 and 2 are sodium, potassium,calcium, strontium and barium; from group 3 are scandium, yttrium, andlanthanum; and from groups 4-15 are titanium, manganese, iron, cobalt,nickel, copper, aluminum, gallium, tin and bismuth.

Examples of combinations falling within sub-group 3 of the metalcombinations are La_(a)Ca_(b)Mn_(c)Co_(d)Ti_(e)O_(x±δ),La_(a)Ca_(b)Co_(c)O_(x±δ), La_(a)Ca_(b)Mn_(c)Ni_(d)O_(x±δ),La_(a)Ca_(b)Mn_(c)Co_(d)Sn_(c)O_(x±δ),La_(a)Ca_(b)Mn_(c)Co_(d)Al_(e)O_(x±δ), La_(a)Ca_(b)Mn_(c)Co_(d)O_(x±δ),Ba_(a)K_(b)Bi_(c)La_(d)O_(x±δ), La_(a)Ca_(b)Mn_(c)Ti_(d)Al_(e)O_(x±δ),La_(a)Ca_(b)Co_(c)Ni_(d)Al_(e)O_(x±δ), La_(a)Ca_(b)Co_(c)Ti_(d)O_(x±δ),La_(a)Ca_(b)Mn_(c)O_(x±δ), Ba_(a)Bi_(b)La_(c)O_(x±δ),La_(a)Ca_(b)Mn_(c)Mg_(d)O_(x±δ), La_(a)Ca_(b)Mn_(c)Fe_(d)O_(x±δ),La_(a)Sr_(b)Co_(c)Al_(d)O_(x±δ), Ba_(a)Bi_(b)Yb_(c)O_(x±δ),La₈Ca_(b)Mn_(c)Ga_(d)O_(x±δ), La_(a)Ca_(b)Mn_(c)Sn_(d)Al_(e)O_(x±δ),La_(a)Ca_(b)Mn_(c)Cu_(d)O_(x±δ), La_(a)Ca_(b)Mn_(c)Co_(d)Ga_(e)O_(x±δ),La_(a)Ca_(b)Mn_(c)Al_(d)O_(x±δ), La_(a)Ca_(b)Co_(c)Al_(d)O_(x±δ),Ba_(a)Bi_(b)Sn_(c)La_(d)O_(x±δ), La_(a)Ca_(b)Fe_(c)Co_(d)O_(x±δ),La_(a)Ca_(b)Mn_(c)Ni_(e)Al_(f)O_(x±δ), Y_(a)Ca_(b)Mn_(c)O_(x±δ), andSr_(a)Na_(b)Sn_(c)Y_(d)O_(x±δ), where a, b, c, d, e and f each between 0and 1, the sum of a through f equals 1 to 3, x is the sum of a through fplus 1, and δ is the vacancy concentration or excess oxygenconcentration. While oxygen is indicated in the formulae above, it willbe recognized that the positions held by oxygen could be substitutedwith sulfur.

In yet another embodiment of the present invention, the SHC component isa combination of oxygen and/or sulfur with two or more metals fromgroups 4-15 of the Periodic Table of the Elements (hereinafter“sub-group 4”). Within sub-group 4, the preferred metals from groups4-15 are at least two of titanium, zirconium, niobium, molybdenum,tungsten, manganese, iron, cobalt, iridium, nickel, palladium, platinum,copper, zinc, aluminum gallium, indium, germanium, tin, antimony, andbismuth. Even more preferred are titanium, manganese, cobalt, copper,zinc, aluminum, and indium.

Examples of combinations falling within sub-group 4 of the metalcombinations are In_(a)Cu_(b)Mn_(c)O_(x±δ), Mn_(a)Co_(b)O_(x±δ),In_(a)Zn_(b)Mn_(c)Al_(d)O_(x±δ), In_(a)Zn_(b)Mn_(c)O_(x±δ),Mn_(a)Zn_(b)O_(x±δ), Mn_(a)Zn_(b)Al_(c)O_(x±δ), In_(a)Mn_(b)O_(x±δ),In_(a)Mn_(b)Al_(c)O_(x±δ), and Mn_(a)Zn_(b)Ti_(c)O_(x±δ), where a, b, c,and d are each between 0 and 1, the sum of a through d equals 1 to 3,xis the sum of a through d plus 1, and δ is the vacancy concentration orexcess oxygen concentration. While oxygen is indicated in the formulaeabove, it will be recognized that the positions held by oxygen could besubstituted with sulfur.

The remaining component of the SHC component in accordance with theinvention is at least one of sulfur and oxygen. Oxygen is preferred. Itis noted that at least a portion of the sulfur present in a SHCcomponent could be removed in the SHC reaction and replaced by oxygen inthe regeneration process. It is also noted that in embodiments in whichthe hydrocarbon feed contained sulfur compounds, the SHC component couldhave sulfur present in the structure. Therefore, it is likely thatapplications of this invention with sulfur-containing feedstock couldinvolve a SHC component containing both sulfur and oxygen regardless ofwhich is used in the initial formulation of the SHC component.

In a preferred embodiment, the SHC component can adopt a perovskite(ABO₃) crystal structure, a spinel (AB₂O₄) crystal structure, or abirnessite (A_(z)BO_(x)) crystal structure, where A and B are twodistinct metal sites.

In an embodiment with a perovskite crystal structure, each metal sitecan comprise one or more metal cations. The crystal structure can besignificantly distorted from the idealized cubic, perovskite structuredepending on the choice of metals at A and B sites and/or due to theformation of oxygen vacancies upon reduction. In a preferred embodiment,the sum of a through n, in the sample compositions provided above, is 2and X is 3. The A sites in a perovskite structure are coordinated with12 oxygen sites. The B sites in the structure would then be occupied bythe remaining, generally smaller atoms, and are coordinated with 6oxygen sites. Selection of A and B metal cations to optimize theirrelative sizes is desirable for maximum structural stability structure.Different metal cations can be substituted (or doped) at a particularsite, and for stability it is desirable that the size of these cationsbe similar to the size of the cation being replaced. These criteriaallow optimization of the selections within each of the desirablecombinations of metals from selected groups of the Periodic Table.

Stoichiometric perovskites (e.g., A³⁺B³⁺O²⁻ ₃) have all metal and oxygensites occupied, whereas non-stoichiometric perovskites (e.g., A³⁺ _(1−x)A′²⁺ _(x)B³⁺O²⁻ _(3−δ) can exist with oxygen vacancies. Oxygen vacancyconcentration (δ) is governed by charge-neutrality. These oxygenvacancies in the crystal structure provide one mechanism for solid-statediffusion of O²⁻ ions in the crystal lattice. The O²⁻ ions can “jump” or“hop” from occupied sites to vacant sites, and hence diffuse within thelattice. This vacancy hopping mechanism for O²⁻ diffusion has beenestablished in various metal oxide compounds.

The metals are preferably selected to optimize use of oxygen and/orsulfur from the lattice structure as indicated by the relationship belowwhere the presence of reducible metal cations allow oxygen or sulfur tobe removed from the lattice:

O²⁻→½O₂+2e′+V_(O)

M^(n+)+2e′→M^((n−2)+)

where V_(O) denotes an oxygen vacancy formed due to oxygen being removedfrom the lattice, M is the reducible metal cation, and e is an electron(for a p-type material, holes instead of electrons would be used todenote charge-transfer), where sulfur (S) can be substituted for oxygen(O) throughout. If the metals forming the perovskite or spinel do notreduce, oxygen or sulfur will not be removed from the crystal lattice.

High oxygen diffusivity is necessary to allow O²⁻ ions to diffuse frominterior of metal oxide or sulfide particles to the surface where theycan react with hydrogen. As stated above, oxygen diffusivity can beincreased by creating oxygen vacancies, for example by replacing some ofthe trivalent La with divalent Ca in the crystal structure of LaMnO₃. Inaddition to oxygen mobility, electronic conductivity is also essentialto allow electrons (or holes) to be transported away from (or to) theinterface.

For the purposes of this invention, the SHC component will preferablyhave low reactivity towards hydrocarbons. Combinations of metals may beselected to optimize the properties for a given application. Lowermolecular weight materials are generally preferred for the economicbenefit of greater oxygen capacity for a given mass of material to beused in the catalyst system.

Preferred crystal structures for the SHC component would demonstrate anability to sustain oxygen vacancies in crystal structure. Perovskitescan accommodate a large vacancy concentration (δ) as large as 0.5 orhigher without phase decomposition. This phase stability allows forreversible oxygen and/or sulfur removal from and addition to the SHCcomponent.

Another preferred crystal structure is the spinel (AB₂O₄) structurewhere A and B represent two distinct metal cation sites, where “B” isoctahedrally coordinated to 6 oxygen sites and “A” is tetrahedrallycoordinated to 4 oxygen sites.

Another preferred structure is the birnessite (A_(z)BO_(x)) crystalstructure, which generally contains layered manganese oxide (MnO₆ ²⁻)octahedra sheets with “A” cations, typically group 1 or group 2 metalions, incorporated between MnO₆ layers to balance the negative charge onthe sheets. Differing amounts of hydration water can also beincorporated between these layers. The birnessite structure can besynthesized along with the spinel structure, and has been observed totransform to a spinel structure. High-temperature stability ofbirnessite, and its transformation to spinel structure, appears todepend on selection of the stabilizing cation. For example, birnessitestructures containing potassium appear to be more stable than thosecontaining sodium.

It is anticipated that other crystalline structures could also be usedto provide a SHC component capable of surrendering oxygen to a hydrogencombustion reaction.

The catalyst system of the present invention can also include at leastone of at least one support, at least one filler, and at least onebinder. The SHC component could be prepared, by way of non-limitingexample, by combining salts or chalcogenides (compounds of the group 16elements) containing the desired parts through such means as evaporationor precipitation, optionally followed by calcination. The aromatizationcomponent is then physically mixed or chemically reacted with the SHCcomponent, optionally, combined with a binder to form catalystparticles, and as an additional option, may be combined with a carrierto form slurry.

The SHC component can be obtained through chemical means, such as thecombination of metal salts and/or chalcogenides, in solution or slurry,followed by removal of the solvent or mother liquor via evaporation orfiltration and drying. Various methods for synthesizing particularcompounds are known in the art. The SHC component can then be ground andcalcined. The aromatization and SHC components can be physically admixedby mechanical mixing.

The aromatization component and the SHC component of the catalyst systemin accordance with the present invention can be chemically bound. Thechemically bound materials can then be subjected to the treatment of amatrix component. The matrix component serves several purposes. It canbind the aromatization component and the SHC component to form catalystparticles. It can serve as a diffusion medium for the transport of feedand product molecules. It can also act as a filler to moderate thecatalyst activity. In addition, the matrix can help heat transfer orserve as a sink or trap for metal contaminants in the feedstock.

Examples of typical matrix materials include amorphous compounds such assilica, alumina, silica-alumina, silica-magnesia, titania, zirconia, andmixtures thereof. It is also preferred that separate alumina phases beincorporated into the inorganic oxide matrix. Species of aluminumoxyhydroxides-γ-alumina, boehmite, diaspore, and transitional aluminassuch as α-alumina, β-alumina, γ-alumina, δ-alumina, ε-alumina,κ-alumina, and ρ-alumina can be employed. Preferably, the aluminaspecies is an aluminum trihydroxide such as gibbsite, bayerite,nordstrandite, or doyelite. The matrix material may also containphosphorous or aluminum phosphate. The matrix material may also containclays such as halloysite, kaolinite, bentonite, attapulgite,montmorillonite, clarit, fuller's earth, diatomaceous earth, andmixtures thereof. The weight ratio of the aromatization component andthe SHC component to the inorganic oxide matrix component can be about100:1 to 1:100.

In another aspect of the present invention, the aromatization componentand the SHC component may be treated separately with a matrix component.The matrix component for the aromatization component can be the same asor different from that for the SHC component. One of the purposes of thetreatment is to form particles of the aromatization component andparticles of the SHC component so that the components are hard enough tosurvive inter-particle and reactor wall collisions. The matrix componentmay be made according to conventional methods from an inorganic oxidesol or gel, which is dried to “glue” the catalyst particle's componentstogether. The matrix component can be catalytically inactive andcomprises oxides of silicon, aluminum, and mixtures thereof. It is alsopreferred that separate alumina phases be incorporated into theinorganic oxide matrix. Species of aluminum oxyhydroxides-γ-alumina,boehmite, diaspore, and transitional aluminas such as α-alumina,β-alumina, γ-alumina, δ-alumina, ε-alumina, κ-alumina, and ρ-alumina canbe employed. Preferably, the alumina species is an aluminum trihydroxidesuch as gibbsite, bayerite, nordstrandite, or doyelite. The matrixmaterial may also contain phosphorous or aluminum phosphate. The matrixmaterial may also contain clays such as kaolinite, bentonite,attapulgite, montmorillonite, clarit, fuller's earth, diatomaceousearth, and mixture thereof.

The weight ratio of the aromatization component to the matrix componentcan be about 100:1 to 1:100. The weight ratio of the SHC component tothe matrix component can be about 100:1 to 1:100.

In accordance with the present invention, the weight ratio ofaromatization component to the total weight of SHC component is from1000:1 to 1:1000. More preferably, the ratio is from 500:1 to 1:500.Most preferably, the ratio is from 100:1 to 1:100. This ratio can beadjusted and optimized for a given feedstock and desired product slate.

The aromatization component particles and the SHC component particlesmay be mixed to form a uniform catalyst system in the reactor or bepacked in series to form a staged catalyst system in either a singlereactor or two or more staged reactors. Preferably, the catalyst systemcomponents are mixed to form a uniform catalyst system.

Non-Limiting Illustrative Processes

An aspect of the invention relates to a hydrocarbon conversion processusing the inventive catalyst system in any known reactor suitable foraromatization reactions and selective hydrogen combustion reactions. Byway of non-limiting, illustrative example, fixed-bed reactors withcatalyst regeneration, moving bed reactors with catalyst regenerationsuch as the continuous catalyst regeneration reactor (also known asCCR), fluidized-bed processes such as a riser reactor with catalystregeneration and the like would be suitable. Examples of fixed-bedcatalytic reactors include fixed-bed tubular reactors. A non-limitingillustrative example of a suitable fixed-bed catalyst regenerationsystem is illustrated in U.S. Pat. No. 5,059,738 to Beech, Jr. et al,which is incorporated herein by reference in its entirety. Anon-limiting illustrative example of a suitable continuous catalystregeneration moving bed reactor is illustrated in U.S. Pat. No.5,935,415 to Haizmann et al, which is incorporated herein by referencein its entirety.

The overall hydrocarbon conversion processes, i.e., the simultaneous (i)aromatization reactions and (ii) selective hydrogen combustion reactionsare carried out in the presence of catalyst systems, and are believed tobe catalytic processes. The conversion reactions can be carried out attemperatures and pressures effective for converting oxygenatedhydrocarbon to aromatics. For example, the hydrocarbon conversionprocesses are particularly efficient when carried out at reaction zonetemperatures of from 300° C. to 800° C. Alternatively, the overallhydrocarbon conversion process to produce the aromatics is particularlyefficient at reaction zone temperatures of from 300° C. to 600° C., orat temperatures of from 300° C. to 550° C.

The inventive catalyst system must be regenerated with an oxidant toreplenish the lattice oxygen of the SHC component of the catalyst systemand to remove at least a portion of any coke on the catalyst systemcomponents. Regeneration temperatures can be in the range of about 300to about 800° C.

Operating pressures may include a pressure of at least atmosphericpressure (zero pressure, gauge), such as ≥4 pounds per square inch gauge(psig) (28 kilo Pascals gauge (kPag)), or ≥15 psig (103 kPag), or ≥36psig (248 kPag), or ≥44 psig (303 kPag), or ≥103 psig (709 kPag), butmay be ≤300 psig (2064 kPag), or ≤163 psig (1121 kPag), or ≤150 psig(1032 kPag).

Also, as may be appreciated, these different pressures and temperaturesmay be utilized together to form different combinations depending on thespecific configuration of equipment.

A flow-through reactor that would be suitable for use in practicing theinventive process is disclosed in U.S. patent application Ser. No.14/469141, filed Aug. 26, 2014, which is incorporated herein byreference in its entirety.

In certain aspects, the invention relates to a reaction system thatincludes a reactor comprising: (i) a first region having a firstaperture; (ii) a second region having a second aperture, and (iii) acatalytic conversion zone containing a catalyst system comprising (1) atleast one aromatization component and (2) at least one selectivehydrogen combustion (“SHC”) component. The first and second regions canbe configured for flowing an oxidant to enter the reactor proximate tothe first aperture at a first time interval, and for flowing anoxygenated hydrocarbon feed to enter the reactor proximate to the firstaperture at a second time interval, with the first and second timeintervals being at separate time intervals relative to one another. Thefirst and second regions can be further configured to flow one or morecomponents of a reaction mixture to exit the reactor proximate to thesecond aperture.

Optionally, the reactor of the reaction system can be a reverse-flowreactor. For example, the reverse-flow reactor can be configured forflowing an oxidant to enter the reactor proximate to the first apertureat a first time interval (forward direction), and a second flow of anoxygenated hydrocarbon feed to enter the reactor proximate to the secondaperture at a second time interval (reverse direction). The reactor canbe further configured to exit one or more components of a reactionmixture proximate to the first aperture.

Flow-through type reactors are particularly suitable for carrying outthe simultaneous aromatization reactions and selective hydrogencombustion reactions in the presence of the specified catalyst system.As a first step, or during a first time interval, oxidant is passedthrough the flow-through reactor. The flow-through reactor is maintainedunder conditions of temperature, pressure, and flow sufficient toregenerate the components of the catalyst system including (i)transferring oxygen from the oxidant to the selective hydrogencombustion (“SHC”) component, (ii) storing the transferred oxygen withinthe SHC component lattice, and (iii) removing by oxidation or combustionany coke deposits from both the SHC and aromatization components of thecatalyst system.

Optionally, when additional heat is needed, this can be provided to theflow-through reactor by one or more of (i) heating the oxidant upstreamof or in the flow-through reactor, and (ii) introducing a hydrocarbonfuel with the oxidant to combust and exothermically release heat to theflow-through reactor. When the oxidant provides heat to the flow-throughreactor, the oxidant can be referred to as “heating fluid”. Heatingfluid can be utilized, e.g., when the overall hydrocarbon conversionprocess, namely the simultaneous aromatization reactions and selectivehydrogen combustion reactions, is net endothermic.

When the overall hydrocarbon conversion process is net exothermic, heatis removed to maintain the specified conversion conditions. Heat may beremoved via any known method including but not limited to (i) coolingthe oxygenated hydrocarbon feed before it is introduced to the reactoror (ii) cooling the reactor via indirect heat transfer with a coolingmedium.

During the first time interval, oxygen is transferred from the oxidantto the SHC component. Additionally, sufficient oxygen and/or heat ispassed through the reactor to remove from both the aromatizationcomponent and the SHC component of the catalyst system any coke byoxidation or combustion. Oxidant flow is lessened or stopped after (i)sufficient oxygen is stored with the SHC catalyst for carrying out theselective hydrogen combustion (ii) sufficient heat is added (if any isneeded) for carrying out the hydrocarbon conversion process, and (iii)sufficient coke is removed.

During a subsequent or second time interval, oxygenated hydrocarbon feedis passed through the flow-through reactor under conditions of pressure,temperature and flow sufficient for aromatizing at least a portion ofthe oxygenated hydrocarbon feed. As the oxygenated hydrocarbon feedflows through the reactor, at least a portion of the oxygenatedhydrocarbon feed is aromatized producing aromatics and hydrogen, amongother products, in the presence of at least the aromatization componentof the catalyst system. Simultaneously, at least a portion of theproduced hydrogen reacts with the stored oxygen in the SHC component ofthe catalyst system to form water.

The aromatization of the oxygenated hydrocarbon feed in the presence ofthe aromatization component of the catalyst system and the combustion ofthe produced hydrogen with the SHC stored oxygen oxidant in the presenceof the SHC component of the catalyst system produces a reaction mixturecomprising (i) aromatics and (ii) water.

Oxidant and oxygenated hydrocarbon feed can be flowed in the samedirection in the flow-through reactor (“uni-flow”), provided each flowis carried out during separate time intervals. For example, during afirst time interval an oxidant can be flowed in a forward direction.During a second or subsequent time interval, the oxygenated hydrocarbonfeed can be flowed in the forward direction through the flow-throughreactor.

If desired, a sweep fluid can be passed through the flow-through reactorduring a time interval between the first time interval and the secondtime interval. The sweep fluid can be passed in the forward direction orthe reverse direction. Typical sweep fluids include relatively inertliquids and vapors, especially those which are relatively easy toseparate from the aromatics products. Steam and/or molecular nitrogenare examples of suitable sweep fluids.

Reverse-flow catalytic reactors can be used to carry out the catalytichydrocarbon conversions, including one or more conventional reverse-flowreactors. Reactors typically used for converting reactions, and toexecute cyclic, high temperature chemistry, can be used, such as thosedescribed in U.S. Pat. Nos. 7,943,808, 7,491,250, 7,846,401, and7,815,873.

Generally, forward and reverse flows through reverse-flow catalyticreactors are carried out during separate time intervals. For example,oxidant can be flowed in a first or forward direction through thereverse-flow reactor, during a first time interval. During a second orsubsequent time interval, oxygenated hydrocarbon feed can be flowed in asecond or reverse direction through the reverse-flow reactor.

Regenerative, reverse-flow catalytic reactors can be used to carry out(i) the aromatization reactions and (ii) the selective hydrogencombustion reactions. A regenerative, reverse-flow reactor is (i)“reverse flow” in the sense that an upstream region of the reactor withrespect to the average flow of the first feed mixture corresponds to thedownstream region with respect to the average flow of the second feedmixture and (ii) “regenerative” in the sense that at least a portion ofany heat lost during a time interval is restored by heat released duringa subsequent interval (and vice versa). Regenerative, reverse-flowreactors may be particularly advantageous when the overall hydrocarbonconversion process is net endothermic.

A variety of flow-through reactors are suitable. The flow-throughreactor can be physically symmetric, e.g., a reverse-flow reactor thatis symmetric about a central axis. The flow-through reactor can beadiabatic, e.g., an adiabatic reverse-flow reactor. The flow-throughreactor can include a housing, a plurality of flow-control means (e.g.,conduits and valves), one or more insulation components (e.g.,insulation bricks) and one or more process flow components (e.g.,thermal mass, mixing components, etc.). The housing may be utilized toenclose an interior region and has one or more insulation componentsdisposed adjacent to the housing. The plurality of flow control meansmay include one or more conduits, one or more apertures, and one or morevalves that are configured to manage the flow of one or more streamsinto and out of the interior region from a location external to theinterior region or housing. Process flow components can be configuredand/or arranged to manage the flow of fluids through the interiorregion.

Regenerative reverse-flow reactors may involve multiple steps repeatedin sequence to form a cycle for the process. For example, the processcan include two or more sequential steps, such as two or more stepsoperated continuously in sequence (one step after the other). The stepscan include, e.g., (i) a net endothermic, forward-flow oxygentransfer/storage and reactor regeneration step, (ii) a net exothermic,reverse-flow, hydrocarbon conversion step, (iii) a repetition of theforward-flow oxygen transfer/storage and reactor regeneration step, and(iv) a repetition of the reverse-flow hydrocarbon conversion step. Aspart of these steps, valves may be utilized to alternate introduction offeed mixtures into the reactor, e.g., a first feed mixture comprisingoxidant and a second feed mixture comprising oxygenated hydrocarbonfeed.

A first feed stream to the flow-through reactor includes oxidant(optionally as a heating fluid or a component thereof), which can bepassed to the flow-through reactor at a first time interval. A secondfeed stream to the flow-through reactor includes oxygenated hydrocarbon,which can be passed to the flow-through reactor at a second timeinterval.

Using continuous catalyst regeneration technology would also overcomethe potential problem related to lattice oxygen being quickly consumedwith resultant loss of catalyst activity. A fluidized bedreactor-regenerator system is a suitable continuous catalystregeneration technology for carrying out the hydrocarbon conversionprocess. A non-limiting example of such a reactor system is adowner-regenerator or a riser-regenerator system as described below forillustration purposes only. A riser-regenerator system that would besuitable for use in practicing the inventive process is disclosed inU.S. Pat. No. 5,002,653, which is incorporated herein by reference inits entirety.

In a riser-regenerator system, oxygenated hydrocarbon feed is contactedwith the inventive catalyst system in a feed riser line (a reactionzone) wherein the simultaneous aromatization and selective hydrogencombustion conversion reactions primarily take place. The catalyst tooxygenated hydrocarbon feed ratio, weight basis, can be in the range of0.01 to 1000. The residence time in the reaction zone can be in therange of 0.01 second to 10 hours. Though not required, it is preferredthat the feed's residence time in the reaction zone be less than about100 seconds, for example from about 0.01 to about 60 seconds, preferablyfrom about 0.1 to about 30 seconds.

As the conversion reactions progress, the catalyst system isprogressively deactivated primarily by consumption of lattice oxygenfrom the SHC component but also by the formation of coke on allcomponents of the catalyst system surface. The catalyst system andconversion products are separated mechanically and any hydrocarbonsremaining on the catalyst are removed by steam stripping before thecatalyst system enters a catalyst regenerator. The conversion productsare taken overhead to a series of fractionation towers for productseparation. The at least partially deactivated catalyst system isreactivated in the regeneratorby introducing an oxidant, such as air, toreplenish the catalyst system's lattice oxygen consumed in the reactor.The introduction of oxidant also burns off any coke deposits on thecatalyst system. As required, a small amount of fresh make-up catalystsystem can be added to the reactor or, preferably, to the regenerator.

The hydrocarbon conversion process of the present invention may also beperformed in one or more conventional FCC process units in the presenceof the catalyst system of this invention. Each unit comprises a riserreactor having a reaction zone, a stripping zone, a catalystregeneration zone, and at least one fractionation zone. The oxygenatedhydrocarbon feed is conducted to the riser reactor where it is injectedinto the reaction zone wherein the feed contacts a flowing sourceregenerated catalyst. The catalyst aromatizes the feed and selectivelycombusts the resultant hydrogen. The aromatization reaction may depositcarbonaceous hydrocarbons, or coke, on the catalyst system and theselective hydrogen combustion reaction depletes the lattice oxygen ofthe SHC component, thereby at least partially deactivating the catalystsystem. The conversion products may be separated from the partiallydeactivated catalyst system and a portion of the conversion products maybe fed to a fractionator. The fractionator generally separates at leasta fraction comprising aromatics from the conversion products.

The deactivated catalyst system flows through the stripping zone wherevolatile hydrocarbons are stripped from the catalyst particles with astripping material such as steam. The stripped catalyst is thenconducted to the regeneration zone where it is regenerated by burningany coke on the catalyst system and replenishing the oxygen-depleted SHCcatalyst component in the presence of an oxidant, preferably air.Decoking and oxidation restore catalyst activity. The catalyst is thenrecycled to the riser reactor at a point near or just upstream of thereaction zone. Flue gas formed by burning coke in the regenerator may betreated for removal of particulates and for conversion of carbonmonoxide, after which the flue gas is normally discharged into theatmosphere.

The overall hydrocarbon conversion may be net exothermic or netendothermic. When the hydrocarbon conversion is net endothermic, thestripping may be performed under low severity conditions in order toretain absorbed hydrocarbons for heat balance through combustion in theregenerator. The heat from combustion is transferred to the catalystsystem and heated catalyst is carried to the reaction zone.Alternatively, when the hydrocarbon conversion is net exothermic, heatmay be removed by any conventional method. A suitable method of heatremoval is the addition of catalyst coolers to the reactor system. Anon-limiting example of catalyst coolers is described in U.S. Pat. No.4,328,384 which is incorporated here by reference in its entirety. Aslip stream of catalyst is withdrawn from the fluidized reactor system.The catalyst is indirectly cooled by a cooling medium, such as water, asthe catalyst passes downward through the catalyst cooler. Stripping gas,such as steam, is introduced counter-current to the catalyst flow andstrips volatile hydrocarbons from the catalyst. The stripping gas andvolatile hydrocarbons exit the top of the catalyst cooler and arereintroduced to the reactor system. Cooled catalyst exits the bottom ofthe catalyst cooler and is reintroduced into the fluidized reactorsystem, for example, at the riser reaction zone. Catalyst coolers couldbe added to the riser reactor, regenerator, or both.

EXAMPLES

The invention is illustrated in the following non-limiting examples,which are provided for the purpose of representation, and are not to beconstrued as limiting the scope of the invention. All parts andpercentages in the examples are by weight unless indicated otherwise.

Example 1

Certain embodiments of the invention are depicted in FIG. 1. FIG. 1illustrates a flow-through reactor, for example a catalytic reverse-flowreactor having a first region 1 and a second region 2. The reaction zone3 contains the catalyst system, comprising at least one SHC componentand at least one aromatization component. The invention, however, is notlimited to catalytic reverse-flow reactors having two regions.

An example of the hydrocarbon conversion process for producing anaromatics composition can be described with reference to FIG. 1. Duringa first step of the process for producing the aromatics composition, orduring a first time interval, oxidant is passed through the flow-throughreactor in a forward direction, as shown by the direction of the arrow.Oxygen from the oxidant is stored with the SHC component of the catalystsystem in reaction zone 3 as the oxidant is passed through the reactor.At least a portion of any coke on or in the reactor or the catalystsystem is removed via combustion or oxidation with the oxygen from theoxidant. Over a desired cycle time, the flow of the heating fluid isstopped.

During a second time interval, a feed containing ≥10.0 wt. % oxygenatedhydrocarbon (e.g., methanol), based on total weight of the feedstream,is passed through the flow-through reactor. The feed passes across orthrough reaction zone 3, with at least a portion of the oxygenatedhydrocarbon in the feed being aromatized in the presence of thearomatization component of the catalyst system to produce aromatics andhydrogen, among other products. Simultaneously, the produced hydrogen isselectively combusted or oxidized in the presence of oxygen stored inthe SHC component of the catalyst system. This results in a conversionmixture comprising an aromatics product composition. The conversionmixture can be conducted away from the reactor for further processing,such as separation of aromatics from other conversion products.

The oxidant and oxygenated hydrocarbon feed can be flowed in the samedirection (i.e., a forward direction as shown by the arrow of FIG. 1) aslong as the flows are at separate time intervals. For example, theoxidant can be flowed in a forward direction through the flow-throughreactor, during a first time interval. During a second or subsequenttime interval, the hydrocarbon reactant also can be flowed in theforward direction through the flow-through reactor.

The flow-through reactor of FIG. 1 can be operated as a reverse-flowreactor, with the oxidant/regeneration step being carried out in a firsttime interval and the hydrocarbon conversion step being carried out in asecond time interval. When the process is carried out in a reverse-flowarrangement, oxidant and oxygenated hydrocarbon feed are flowed inopposite directions through the reverse-flow reactor at separate timeintervals.

As shown in FIG. 1, the heating fluid is flowed in a first or forwarddirection through the flow-through reactor, during a first timeinterval. When the flow-through reactor is operated in a reverse-flowarrangement, during a second or subsequent time interval, the oxygenatedhydrocarbon feed is flowed in a second or reverse direction of the arrowshown in FIG. 1.

The first and second time intervals, as generally described according tothe exemplary scheme shown in FIG. 1, can be substantiallynon-overlapping intervals. Each of the first and second time intervalscan be, independently, an interval having a duration in the range offrom about 0.5 seconds to about 15 seconds. The interval between thefirst and second time intervals (the “dead-time”, which represents theinterval of time it takes to reverse flow of the feed mixtures) ispreferably as short as possible so that the reverse flow cycle can be asrapid as possible. From a practical standpoint, the dead-time should be,e.g., ≤than 0.5 seconds, such as in a range of from about 0.01 secondsto about 0.5 seconds. Upon completion of the second time interval, theintervals can be repeated. That is, the flow shown in FIG. 1 can bereinitiated and followed by subsequent re-initiation of the flow shownin FIG. 1.

In the exemplary embodiment shown in FIG. 1, the oxidant can comprise≥90.0 wt. % of O₂, e.g., O₂ obtained from air, based on total weight ofthe oxidant. The oxygenated hydrocarbon feed can comprise ≥80 wt. %methanol.

What is claimed is:
 1. A catalyst system comprising: (1) at least onearomatization component for converting oxygenated hydrocarbons toaromatic compounds and (2) at least one selective hydrogen combustioncomponent for reacting hydrogen with oxygen, said selective hydrogencombustion component consisting essentially of (a) a metal combinationselected from the group consisting of: i) at least one metal from group3 and at least one metal from groups 4-15 of the Periodic Table of theElements; ii) at least one metal from groups 5-15 of the Periodic Tableof the Elements, and at least one metal from at least one of groups 1,2, and 4 of the Periodic Table of the Elements; iii) at least one metalfrom groups 1-2, at least one metal from group 3, and at least one metalfrom groups 4-15 of the Periodic Table of the Elements; and iv) two ormore metals from groups 4-15 of the Periodic Table of the Elements and(b) at least one of oxygen and sulfur, wherein the at least one ofoxygen and sulfur is chemically bound both within and between themetals.
 2. The catalyst system of claim 1, wherein the selectivehydrogen combustion component is a combination of metal combination(a)(i) and (b) at least one of oxygen and sulfur.
 3. The catalyst systemof claim 2, wherein the at least one selective hydrogen combustioncomponent comprises one or more of Y_(a)In_(b)Zn_(c)Mn_(d)O_(x±δ),La_(a)Mn_(b)Ni_(c)Al_(d)O_(x±δ), La_(a)Mn_(b)Al_(c)O_(x±δ),Sc_(a)Cu_(b1)Mn_(c)O_(x±δ), Sc_(a)Zn_(b)Mn_(c)O_(x±δ),La_(a)Zr_(b)O_(x±δ), Mn_(a)Sc_(b)O_(x±δ), and Pr_(a)In_(b)Zn_(c)O_(x±δ),where a, b, c, and d are each between 0 and 1, the sum of a through dequals 1 to 3, x is the sum of a through d plus 1, and δ is the vacancyconcentration or excess oxygen concentration.
 4. The catalyst system ofclaim 1, wherein the selective hydrogen combustion component is acombination of metal combination (a)(ii) and at least one of oxygen andsulfur.
 5. The catalyst system of claim 4, wherein the at least oneselective hydrogen combustion component comprises one or more ofK_(a)Ba_(b)Mn_(c)O_(x±δ), K_(a)Mg_(b)Mn_(c)O_(x±δ),Na_(a)Mg_(b)Mn_(c)O_(x±δ), Mn_(a)Mg_(b)O_(x±δ),K_(a)Sr_(b)Mn_(c)O_(x±δ), In_(a)Ca_(b)Mn_(c)O_(x±δ),Bi_(a)Ca_(b)Mn_(c)Co_(d)O_(x±δ), Bi_(a)Ca_(b)Mn_(c)Ni_(d)O_(x±δ),Ca_(a)Mn_(b)Sn_(c)Co_(d)O_(x±δ), In_(a)Mg_(b)Mn_(c)Al_(d)O_(x±δ),In_(a)Zn_(b)Mn_(c)Al_(d)O_(x±δ), Na_(a)Ba_(b)Mn_(c)O_(x±δ),Na_(a)Co_(b)Mn_(c)O_(x±δ), Ca_(a)Mn_(b)Sb_(c)O_(x±δ),Ca_(a)Mn_(b)Co_(c)Al_(d)O_(x±δ), Sr_(a)Sb_(b)Sn_(c)Mg_(d)O_(x±δ),K_(a)Co_(b)Mn_(c)O_(x±δ), Mn_(a)Mg_(b)O_(x±δ),Ni_(a)Mg_(b)Mn_(c)O_(x±δ), Mn_(a)Mg_(b)Al_(c)O_(x±δ),Mn_(a)Mg_(b)Ti_(c)O_(x±δ), Sr_(a)Sb_(b)Ca_(c)O_(x±δ),Sr_(a)Ti_(b)Sn_(c)Al_(d)O_(x±δ), Sr_(a)Mn_(b)Ti_(c)Al_(d)O_(x±δ),Ca_(a)Mn_(b)O_(x±δ), Ca_(a)Mn_(b)O_(x±δ), Ca_(a)Znr_(b)Al_(c)O_(x±δ),Bi_(a)Ca_(b)Mn_(c)O_(x±δ), Bi_(a)Sr_(b)Co_(c)Fe_(d)O_(x±δ),Ba_(a)Mn_(b)O_(x±δ), Ca_(a)Mn_(b)Al_(c)O_(x±δ),Ca_(a)Na_(b)Sn_(c)O_(x±δ), and Ba_(a)Zr_(b)O_(x±δ), where a, b, c, and dare each between 0 and 1, the sum of a through d equals 1 to 3, x is thesum of a through d plus 1, and δ is the vacancy concentration or excessoxygen concentration.
 6. The catalyst system of claim 1, wherein theselective hydrogen combustion component is a combination of metalcombination (a)(iii) and at least one of oxygen and sulfur.
 7. Thecatalyst system of claim 6, wherein the at least one selective hydrogencombustion component comprises one or more ofLa_(a)Ca_(b)Mn_(c)Co_(d)Ti_(e)O_(x±δ),La_(a)Ca_(b)Mn_(c)Co_(d)Sn_(e)O_(x±δ), La_(a)Ca_(b)Co_(c)O_(x±δ),La_(a)Ca_(b)Mn_(c)Ni_(d)O_(x±δ), La_(a)Ca_(b)Mn_(c)Co_(d)Sn_(e)O_(x±δ),La_(a)Ca_(b)Mn_(c)Co_(d)Al_(e)O_(x±δ), La_(a)Ca_(b)Mn_(c)Co_(d)O_(x±δ),Ba_(a)K_(b)Bi_(c)La_(d)O_(x±δ), La_(a)Ca_(b)Mn_(c)Ti_(d)Al_(e)O_(x±δ),La_(a)Ca_(b)Co_(c)Ni_(d)Al_(e)O_(x±δ), La_(a)Ca_(b)Co_(c)Ti_(d)O_(x±δ),La_(a)Ca_(b)Mn_(c)O_(x±δ), Ba_(a)Bi_(b)La_(c)O_(x±δ),La_(a)Ca_(b)Mn_(c)Mg_(d)O_(x±δ), La_(a)Ca_(b)Mn_(c)Fe_(d)O_(x±δ),La_(a)Sr_(b)Co_(c)Al_(d)O_(x±δ), Ba_(a)Bi_(b)Yb_(c)O_(x±δ),La₈Ca_(b)Mn_(c)Ga_(d)O_(x±δ), La_(a)Ca_(b)Mn_(c)Sn_(d)Al_(e)O_(x±δ),La_(a)Ca_(b)Mn_(c)Cu_(d)O_(x±δ), La_(a)Ca_(b)Mn_(c)Co_(d)Ga_(e)O_(x±δ),La_(a)Ca_(b)Mn_(c)Al_(d)O_(x±δ), La_(a)Ca_(b)Co_(c)Al_(d)O_(x±δ),Ba_(a)Bi_(b)Sn_(c)La_(d)O_(x±δ),La_(a)Ca_(b)Mn_(c)Co_(d)Ni_(e)Al_(f)O_(x±δ), Y_(a)Ca_(b)Mn_(c)O_(x±δ),La_(a)Ca_(b)Fe_(c)Co_(d)O_(x±δ), and Sr_(a)Na_(b)Sn_(c)YH_(d)O_(x±δ),where a, b, c, d, e and f are each between 0 and 1, the sum of a throughf equals 1 to 3, x is the sum of a through f plus 1, and δ is thevacancy concentration or excess oxygen concentration.
 8. The catalystsystem of claim 1, wherein the selective hydrogen combustion componentis a combination of metal combination (a)(iv) and at least one of oxygenand sulfur.
 9. The catalyst system of claim 8, wherein the at least oneselective hydrogen combustion component comprises one or more ofIn_(a)Cu_(b)Mn_(c)O_(x±δ), Mn_(a)Co_(b)O_(x±δ),In_(a)Zn_(b)Mn_(c)Al_(d)O_(x±δ), In_(a)Zn_(b)Mn_(c)O_(x±δ),Mn_(a)Zn_(b)O_(x±δ), Mn_(a)Zn_(b)Al_(c)O_(x±δ), In_(a)Mn_(b)O_(x±δ),In_(a)Mn_(b)Al_(c)O_(x±δ), and Mn_(a)Zn_(b)Ti_(c)O_(x±δ), where a, b, c,and d are each between 0 and 1, the sum of a through d equals 1 to 3, xis the sum of a through d plus 1, and δ is the vacancy concentration orexcess oxygen concentration.
 10. The catalyst system of claim 1, whereinthe selective hydrogen combustion component comprises at least onecrystal structure selected from perovskite crystal structure, spinelcrystal structure, or birnessite crystal structure.
 11. The catalystsystem of claim 1, wherein the aromatization component and/or theselective hydrogen combustion component further comprises at least oneof at least one support, at least one filler and at least one binder.12. The catalyst system of claim 1, wherein the aromatization componentcomprises (i) at least one zeolite molecular sieve and, optionally, (ii)a group 8-14 element or a combination of metals from the same group ofthe Periodic Table.
 13. The catalyst system of claim 1, wherein thearomatization component is in physical admixture with the selectivehydrogen combustion component.
 14. The catalyst system of claim 1,wherein the aromatization component and the selective hydrogencombustion component are chemically bound.